Olefin Polymerisation Catalyst Containing a Cycloakane Dicarboxylate as Electron Donor

ABSTRACT

A catalyst system useful in polymerizing olefins comprising a solid, hydrocarbon-insoluble catalyst component containing magnesium, titanium and halogen and an internal or external electron donor comprising a substituted hydrocarbyl four to eight-membered cycloalkane dicarboxylate wherein the substituents are positioned on the cycloalkane to place the dicarboxylate groups into adjacent conformational positions and wherein the substitutes contain 1 to 20 carbon atoms and may be joined to the cycloalkane structure to form a bicyclo structure.

FIELD OF THE INVENTION

This invention relates to components useful in propylene polymerizationcatalysts, and particularly relates to electron donor components used incombination with magnesium-containing supported titanium-containingcatalyst components.

BACKGROUND OF THE INVENTION

Use of solid, transition metal-based, olefin polymerization catalystcomponents is well known in the art including such solid componentssupported on a metal oxide, halide or other salt such aswidely-described magnesium-containing, titanium halide-based catalystcomponents. Such catalyst components are referred to as “supported.”Although many polymerization and copolymerization processes and catalystsystems have been described for polymerizing or copolymerizingalpha-olefins, it is advantageous to tailor a process and catalystsystem to obtain a specific set of properties of a resulting polymer orcopolymer product. For example, in certain applications, a combinationof high activity, stereospecificity are required together with polymercharacteristics such as good morphology, desired particle sizedistribution, acceptable bulk density, molecular weight distribution,and the like.

Typically, supported catalyst components useful for polymerizingpropylene and higher alpha-olefins as well as for polymerizing propyleneand higher olefins with a minor amounts of ethylene and otheralpha-olefins contain an electron donor component as an internalmodifier. Such internal modifier is an integral part of the solidsupported component as is distinguished from an external electron donorcomponent, which together with an aluminum alkyl component, comprisesthe catalyst system. Typically, the external modifier and aluminum alkylare combined with the solid supported component shortly before thecombination is contacted with an olefin monomer.

Selection of the internal modifier can affect catalyst performance andthe resulting polymer formed from a catalyst system. As stated above, itis advantageous and an advance in the art to discover internal modifiersincluding combinations of modifiers which, when incorporated into asupported catalyst, produce desired effects on the polymerizationprocess and the polymer produced.

Generally, organic electron donors have been described as useful inpreparation of the stereospecific supported catalyst componentsincluding organic compounds containing oxygen, nitrogen, sulfur, and/orphosphorus. Such compounds include organic acids, organic acidanhydrides, organic acid esters, alcohols, ethers, aldehydes, ketones,amines, amine oxides, amides, thiols, various phosphorus acid esters andamides, and the like. Mixtures of organic electron donors have beendescribed as useful in incorporating into supported catalyst components.Examples of organic electron donors include dicarboxy esters such asalkyl phthalate and succinate esters.

Examples of substituted succinate ester and cyclohexane dicarboxylateelectron donors are described in U.S. Pat. Nos. 4,442,276 and 4,952,649,European Published Application 86,288, and PCT Published Application WO00/63261, all incorporated by reference herein.

Numerous individual processes or process steps have been disclosed toproduce improved supported, magnesium-containing, titanium-containing,electron donor-containing olefin polymerization or copolymerizationcatalysts. For example, Arzoumanidis et al., U.S. Pat. No. 4,866,022,incorporated by reference herein, discloses a method for forming anadvantageous alpha-olefin polymerization or copolymerization catalyst orcatalyst component which involves a specific sequence of specificindividual process steps such that the resulting catalyst or catalystcomponent has exceptionally high activity and stereospecificity combinedwith very good morphology. A solid hydrocarbon-insoluble, alpha-olefinpolymerization or copolymerization catalyst or catalyst component withsuperior activity, stereospecificity and morphology characteristics isdisclosed as comprising the product formed by 1) forming a solution of amagnesium-containing species from a magnesium hydrocarbyl carbonate ormagnesium carboxylate; 2) precipitating solid particles from suchmagnesium-containing solution by treatment with a transition metalhalide and an organosilane; 3) reprecipitating such solid particles froma mixture containing a cyclic ether; and 4) treating the reprecipitatedparticles with a transition metal compound and an electron donor.

Arzoumanidis et al., U.S. Pat. No. 4,540,679, incorporated by referenceherein, discloses a process for the preparation of a magnesiumhydrocarbyl carbonate by reacting a suspension of a magnesium alcoholatein an alcohol with carbon dioxide and reacting the magnesium hydrocarbylcarbonate with a transition metal component.

Arzoumanidis et al., U.S. Pat. No. 4,612,299, incorporated by referenceherein, discloses a process for the preparation of a magnesiumcarboxylate by reacting a solution of a hydrocarbyl magnesium compoundwith carbon dioxide to precipitate a magnesium carboxylate and reactingthe magnesium carboxylate with a transition metal component.

Particular uses of propylene polymers depend upon the physicalproperties of the polymer, such as molecular weight, viscosity,stiffness, flexural modulus, and polydispersity index (molecular weightdistribution (M_(w)/M_(n))). In addition, polymer or copolymermorphology often is critical and typically depends upon catalystmorphology. Good polymer morphology generally involves uniformity ofparticle size and shape, resistance to attrition and an acceptably highbulk density. Minimization of very small particles (fines) typically isimportant especially in gas-phase polymerizations or copolymerizationsin order to avoid transfer or recycle line pluggage. A particularlyadvantageous polymer for certain uses would have a broadenedpolydispersity index, preferably above about 5, more preferably aboveabout 6, and may be above 7, while maintaining an acceptable flexuralmodulus, preferably above about 1800, more preferably above about 2000MPa, and may be above 2400 MPa.

SUMMARY OF THE INVENTION

A solid, hydrocarbon-insoluble, catalyst component useful inpolymerizing olefins containing magnesium, titanium, and halogen furthercontains an internal electron donor comprising a substituted hydrocarbyl4-8 membered cycloalkane' dicarboxylate wherein the substituents arepositioned on the cycloalkane to place the dicarboxylate groups intoconformational proximity positions and wherein the substitutes contain 1to 20 carbon atoms and may be joined to the cycloalkane structure toform a bicyclo structure.

DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Supported catalyst components of this invention contain at least oneinternal electron donor comprising a substituted hydrocarbyl 4-8membered cycloalkane dicarboxylate wherein the substituents arepositioned on the cycloalkane to place the dicarboxylate groups intoconformational proximity positions and wherein the substitutes contain 1to 20 carbon atoms and may be joined to the cycloalkane structure toform a bicyclo structure.

Typical electron donor compounds of this invention are alkyl esters ofsubstituted cycloalkane dicarboxylic acids, in which the alkyls contain1 to about 20 carbon atoms. Such alkyls typically contain at least twoand preferably at least three carbon atoms. Suitable alkyls also maycontain up to 12 and, typically, up to 8 carbon atoms. Other suitablealkyls contain from 4 to 6 carbon atoms. Typical examples of alkylesters useful in this invention include ethyl, propyl, isopropyl,n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, hexyl,2-ethylhexyl, and octyl, esters. Especially suitable alkyls areisopropyl, n-butyl, and s-butyl.

Although, typically, the alkyl groups forming alkyl dicarboxylic acidesters of this invention are the same, the invention includes alkyldicarboxylic acid esters having different alkyl groups.

In alkyl dicarboxylic acid esters of this invention, the carboxylategroups are placed in conformational proximity positions. Preferably,such carboxylate groups are attached to adjacent carbon atoms forming analkyl cycloalkane 1,2 dicarboxylate. In another aspect of the invention,such carboxylate groups may form a cycloalkane 1,3 dicarboxylate and thelike where the carboxylate groups are not on adjacent carbon atoms. Inany case, the conformational structure of the cycloalkane is constrainedby substituent groups (or chemical bonds in the case of bicyclostructures) such that the carboxylate groups are placed inconformational proximity positions. A structure is constrained when bondrotation or ring conformation change is restricted such that aparticular conformation is preferred.

Substituent groups that are sufficiently bulky to constrain a ringconformation change typically contain at least 3 carbon atoms, althoughgroups containing compatible heteroatoms such as nitrogen, sulfur,silicon, and the like may contain at least one carbon atom. Typically,such bulky substituent groups contain up to 20 carbon atoms and maycontain up to 12 carbon atoms. Typically suitable bulky substituentgroups are isopropyl, isobutyl, t-butyl, s-butyl, isopentyl, isohexyl,2-ethylhexyl, and the like. Compounds of this invention may contain oneor more of such bulky substituent group. Multiple bulky groups may besubstituents to produce a constrained conformational structure.

Alkyl groups used in this invention also may be substituted withcompatible groups containing heteroatoms including silicon and halogens.

Typical examples of these compounds are represented by the substitutedcyclohexane:

in which one X and one Y are carboxylate (CO₂R) groups, wherein R isselected from lower alkyl groups containing 1 to 20 carbon atoms; R₁-R₈are selected from bulky and non-bulky alkyl or substituted alkyl groupsto produce a ring conformation that places the carboxylate groups intoproximity; and remaining the X and Y groups are selected from hydrogenand methyl, and provided two of the R₁-R₈ groups may be connected toform a bicycio structure.

Preferably, for non-bicyclo structures, the carboxylate groups are transand R₁ and R₄ are selected from bulky groups. Preferably, the non-bulkygroups are hydrogen.

Other representations of these substituted cyclohexanes demonstratingconformation of the carboxyl groups is:

in which R is selected from lower alkyl groups containing 1 to 20 carbonatoms, at least one of R₁ and R₄ are selected from bulky groupssufficient to place the carboxyl groups into conformational proximitypositions, and R₂ and R₄ are selected from hydrogen and methyl. Theremaining substituents on such a ring structure usually are hydrogen,but may be other compatible groups that produce the desired ringconformation.

in which R is selected from lower alkyl groups containing 1 to 20 carbonatoms, at least one of R₁, R₃, and R₆ are selected from bulky groupssufficient to place the carboxyl groups into conformational proximitypositions, and R₂, R₄, and R₅ are selected from hydrogen and methyl. Theremaining substituents on such a ring structure usually are hydrogen,but may be other compatible groups that produce the desired ringconformation.

Representations of bicyclo compounds of this invention are:

A representation of a cyclopentane of this invention is:

in which R1 and R2 are selected to place the carboxylate groups intoconformational proximity.

In one aspect of this invention, carboxylate groups are positioned ontocycloalkyl structures such that at least two carboxylate groups are inconformational proximity, i.e. at the preferred confirmation of thecycloalkyl ring structure, the carboxylate groups will be spaced closeenough to experience van der Waals repulsion between the groups. Suchrepulsion typically is sufficient that would place the ring into anotherpreferred conformation if the ring conformation was not otherwiseconstrained.

In another aspect of this invention, the carboxylate groups are spacedat least as proximate as corresponding phthalate carboxylate groups.

An example of conformational proximate carboxylate groups aretrans-di-n-butyl-4,5-di-isopropylcyclohexane trans-dicarboxylate andtrans-diisopropyl 4,5-di-t-butylcyclohexane trans-dicarboxylate:

In these structures, spatially bulky tertiary-butyl and isopropyl groupsare in a trans configuration on the cyclohexane ring, which inhibitsring reversal and produces a preferred confirmation in which the bulkygroups are in the equatorial positions on the cyclohexane ring. Theresult is to place the carboxylate groups in equatorial positions, whichare in conformational proximity.

Below are summarized general methods which can be used to prepare thedonors which are described. The first method entails hydrogenation of anappropriately substituted aromatic diacid followed by esterification.The second method employs first a Diels-Alder reaction of a substituteddiene and maleic anhydride to form the substituted cyclohexenestructure. After hydrogenation and esterification the substituted cyclicdiester is formed. The bicyclic compounds can be formed by the thirdroute employing a Diels-Alder reaction of maleic anhydride and a cyclicdiene to form the bicyclic structure. Hydrogenation and esterificationwould yield the bicyclic diester. These reactions are known in the art.

The routes we are employing to prepare examples of the above are asfollows:

Cyclohexane anhydride was esterified with ethanol and ap-toluenesulfonic acid catalyst to yield the cis diester, which was usedas an internal donor to prepare a catalyst according to the proceduresoutlined above. The cis diester may be epimierized to the morethermodynamically stable trans isomer with sodium ethoxide and ethanoland a catalyst may be prepared as described above.

In a similar route, the methyl-cyclohexane anhydride also was esterifiedas shown below. The product was a mixture of isomers, which is believedto be predominantly a combination of cis fused products. That materialalso was used directly in a catalyst preparation. Also this may beepimerized and subsequently used in a catalyst preparation.

The bicyclic materials may be prepared by first reducing the doublebonds of the purchased anhydrides with n=1 and 2. After esterification,cis fusion appears again to be preserved and a catalyst has beenprepared from the bicyclo[2.2.1] system. and a catalyst may be preparedfrom the bicyclo[2.2.2] system. The bicyclo[2.2.2] system will need tobe treated again with hydrogen to fully reduce the initial double bondbefore proceeding. Both materials will also may be epimerized to thepredicted more stable trans isomers to be used in catalyst preparations.

High activity supported (HAC) titanium-containing components useful inthis invention generally are supported on hydrocarbon-insoluble,magnesium-containing compounds in combination with an electron donorcompound. Such supported titanium-containing olefin polymerizationcatalyst component typically is formed by reacting a titanium (IV)halide, an organic electron donor compound and a magnesium-containingcompound. Optionally, such supported titanium-containing reactionproduct may be further treated or modified by further chemical treatmentwith additional electron donor or Lewis acid species.

Suitable magnesium-containing compounds include magnesium halides; areaction product of a magnesium halide such as magnesium chloride ormagnesium bromide with an organic compound, such as an alcohol or anorganic acid ester, or with an organometallic compound of metals ofGroups I-III; magnesium alcoholates; or magnesium alkyls.

Examples of supported catalysts are prepared by reacting a magnesiumchloride, alkoxy magnesium chloride or aryloxy magnesium chloride with atitanium halide, such as titanium tetrachloride, and furtherincorporation of an electron donor compound. In a preferablepreparation, the magnesium-containing compound is dissolved, or is in aslurry, in a compatible liquid medium, such as a hydrocarbon to producesuitable catalyst component particles.

The possible solid catalyst components listed above only areillustrative of many possible solid, magnesium-containing, titaniumhalide-based, hydrocarbon-insoluble catalyst components useful in thisinvention and known to the art. This invention is not limited to aspecific supported catalyst component.

In a typical supported catalyst of this invention, the titanium tomagnesium atom ratio is above about 0.5 to 1 and may range to about 20to 1. Greater amounts of titanium may be employed without adverselyaffecting catalyst component performance, but typically there is no needto exceed a titanium to magnesium ratio of about 20:1. More preferably,the titanium to magnesium ratio ranges from about 2:1 to about 15:1. Theinternal electron donor components typically are incorporated into thesolid, supported catalyst component in a total amount ranging up toabout 1 mole per gram atom of titanium in the titanium compound, andpreferably from about 0.001 to about 0.6 mole per gram atom of titaniumin the titanium compound. Typical amounts of internal donor are at least0.01 mole per gram atom of titanium, preferably above about 0.05 andtypically above about 0.1 mole per gram atom of titanium. Also,typically, the amount of internal donor is less than 1 mole per gramatom of titanium, and preferably below about 0.5, and more preferablybelow about 0.3 mole per gram atom of titanium.

The internal electron donor material of this invention is incorporatedinto a solid, supported catalyst component during formation of suchcomponent. Typically, such electron donor material is added with, or ina separate step, during treatment of a solid magnesium-containingmaterial with a titanium (IV) compound. Most typically, a solution oftitanium tetrachloride and the internal electron donor modifier materialis contacted with a magnesium-containing material. Suchmagnesium-containing material typically is in the form of discreteparticles and may contain other materials such as transition metals andorganic compounds.

The preferred solid, hydrocarbon-insoluble catalyst or catalystcomponent of this invention for the stereoregular polymerization orcopolymerization of alpha-olefins comprises the product formed by aprocess, which comprises a first step of forming a solution of amagnesium-containing species in a liquid wherein themagnesium-containing species is formed by reacting amagnesium-containing compound with carbon dioxide or sulfur dioxide. Themagnesium-containing compound from which the magnesium-containingspecies is formed is a magnesium alcoholate, a magnesium hydrocarbylalcoholate, or a hydrocarbyl magnesium compound. When carbon dioxide isused, the magnesium-containing species is a hydrocarbyl carbonate or acarboxylate. When sulfur dioxide is employed, the resultingmagnesium-containing species is a hydrocarbyl sulfite (ROSO₂ ⁻) or anhydrocarbyl sulfinate (RSO₂ ⁻).

Generally, magnesium hydrocarbyl carbonate is prepared by reactingcarbon dioxide with a magnesium alcoholate. For example, magnesiumhydrocarbyl carbonate is formed by suspending magnesium ethoxide inethanol and adding carbon dioxide until the magnesium ethoxide dissolvesforming magnesium ethyl carbonate. If, however, the magnesium ethoxidewere suspended in 2-ethylhexanol, magnesium 2-ethylhexyl carbonate,magnesium ethyl carbonate and magnesium ethyl/2-ethylhexyl carbonate maybe formed. If the magnesium ethoxide is suspended in a liquidhydrocarbon or halohydrocarbon which is free of alcohol, the addition ofcarbon dioxide results in the breaking apart of the magnesium ethoxideparticles and the magnesium hydrocarbyl carbonate reaction product doesnot dissolve. The reaction of a magnesium alcoholate with carbon dioxidecan be represented as:

wherein n is a whole number or fraction up to 2, and wherein R is ahydrocarbyl group of 1 to 20 carbon atoms. In addition, a magnesiumalcoholate-containing two different aforesaid hydrocarbyl groups may beemployed. From the standpoint of cost and availability, magnesiumalcoholates which are preferred for use according to this invention arethose of the formula Mg(OR)₂ wherein R is as defined below. In terms ofcatalytic activity and stereospecificity, best results are achievedthrough the use of magnesium alcoholates of the formula Mg(OR′)₂ whereinR′ is an alkyl radical of 1 to about 8 carbon atoms, an aryl radical of6 to about 12 carbon atoms or an alkaryl or aralkyl radical of 7 toabout 12 carbon atoms. Magnesium ethoxide is most preferred.

Specific examples of magnesium alcoholates that are useful according tothis invention include: Mg(OCH₃)₂, Mg(OC₂H₅)₂, Mg(OC₄H₉)₂, Mg(OC₆H₅)₂,Mg(OC₆H₁₃)₂, Mg(OC₉H₁₉)₂, Mg(OC₁₀H₇)₂, Mg(OC₁₂H₉)₂, Mg(OC₁₂H₂₅)₂,Mg(OC₁₆H₃₃)₂, Mg(OC₁₈H₃₇)₂, Mg(OC₂₀H₄₁)₂, Mg(OCH₃)(OC₂H₅),Mg(OCH₃)(OC₆H₁₃), Mg(OC₂H₅)(OC₈H₁₇), Mg(OC₆H₁₃)(OC₂₀H₄₁),Mg(OC₃H₇)(OC₁₀H₇), Mg(OC₂H₄Cl)₂ and Mg(OC₁₆H₃₃)(OC₁₈H₃₇). Mixtures ofmagnesium alcoholates also may be used if desired.

A suitable magnesium hydrocarbyl alcoholate has the formula MgR(OR′)wherein R and R′ are as defined hereinabove for the magnesiumalcoholate. When alcohol is used as the suspending medium for thereaction between the magnesium hydrocarbyl alcoholate and carbon dioxideor sulfur dioxide, the magnesium hydrocarbyl alcoholate is a functionalequivalent of the magnesium alcoholate because the magnesium hydrocarbylalcoholate is converted to the magnesium alcoholate in alcohol. However,when the suspending medium does not contain alcohol, the magnesiumhydrocarbyl alcoholate reacts with carbon dioxide as:

wherein y+x=n≧2 and y=0 for x=n≦1.0.In the case of y+n=2,

is the resulting magnesium-containing species.

When the magnesium compound from which the magnesium-containing speciesis formed is a hydrocarbyl magnesium compound having the formula XMgR,where X is a halogen and R is a hydrocarbyl group of 1 to 20 carbonatoms, the reaction of the hydrocarbyl magnesium compound with carbondioxide forms a magnesium carboxylate and can be represented as follows:

If the hydrocarbyl magnesium compound contains two hydrocarbyl groups,the reaction is represented as:

where R is as defined for X—MgR.

The hydrocarbyl magnesium compounds useful in this invention have thestructure R—Mg-Q wherein Q is hydrogen, halogen or R′ (each R′ isindependently a hydrocarbyl group of 1 to 20 carbon atoms.) Specificexamples of hydrocarbyl magnesium compounds useful in this inventioninclude: Mg(CH₃)₂, Mg(C₂H₅)₂, Mg(C₄H₉)₂, Mg(C₆H₅)₂, Mg(C₆H₁₃)₂,Mg(C₉H₁₉)₂, Mg(C₁₀H₇)₂, Mg(C₁₂H₉)₂, Mg(C₁₂H₂₅)₂, Mg(C₁₆H₃₃)₂,Mg(C₂₀H₄₁)₂, Mg(CH₃)(C₂H₅), Mg(CH₃)(C₆H₁₃), Mg(C₂H₅)(C₈H₁₇),Mg(C₆H₁₃)(C₂₀H₄₁), Mg(C₃H₇)(C₁₀H₇), Mg(C₂H₄Cl)₂ and Mg(C₁₆H₃₃)(C₁₈H₃₇),Mg(C₂H₅)(H), Mg(C₂H₅)(Cl), Mg(C₂H₅)(Br), etc. Mixtures of hydrocarbylmagnesium compounds also can be employed if desired. From the standpointof cost and availability, dihydrocarbyl magnesium compounds preferredfor use in this invention are those of the formula MgR₂ wherein R is asdefined above. In terms of catalytic activity and stereospecificity,best results are achieved through the use of hydrocarbyl magnesiumhalide compounds of the formula MgR′Q′ wherein R′ is an alkyl radical of1 to about 18 carbon atoms, an aryl radical of 6 to about 12 carbonatoms or an alkaryl or aralkyl radical of 7 to about 12 carbon atoms andQ′ is chloride or bromide.

Most preferably, the magnesium-containing compound is a magnesiumalcoholate, and the resulting magnesium-containing species is amagnesium hydrocarbyl carbonate.

For example, a magnesium alcoholate may be used which is prepared byreacting magnesium metal turnings to completion with a lower molecularweight alcohol, such as methanol, ethanol, or 1-propanol, with orwithout a catalyst such as iodine or carbon tetrachloride, to form asolid magnesium alcoholate. Any excess alcohol is removed by filtration,evaporation or decantation. Use as the magnesium-containing compound ofa magnesium alcoholate produced in this manner affords a solution of themagnesium-containing species which has a substantially reducedviscosity.

Diluents or solvents suitable for use in the carbonation of themagnesium compounds to form the magnesium-containing species includealcohols containing from 1 to 12 carbon atoms, non-polar hydrocarbonsand halogenated derivatives thereof, ethers and mixtures thereof thatare substantially inert to the reactants employed and, preferably, areliquid at the temperatures of use. It also is contemplated to conductthe reaction at elevated pressure so that lower-boiling solvents anddiluents can be used even at higher temperatures. Examples of usefulsolvents and diluents include alcohols such as methanol, ethanol, 1- or2-propanol, t-butyl alcohol, benzyl alcohol, the amyl alcohols,2-ethylhexanol and branched alcohols containing 9 or 10 carbon atoms;alkanes such as hexane, cyclohexane, ethylcyclohexane, heptane, octane,nonane, decane, undecane, and the like; haloalkanes such as1,1,2-trichloroethane, carbon tetrachloride, and the like; aromaticssuch as xylenes and ethylbenzene; and halogenated and hydrogenatedaromatics such as chlorobenzene, o-dichlorobenzene,tetrahydronaphthalene and decahydronaphthalene.

The solution of the magnesium-containing species typically comprises atleast one monohydroxy alcohol containing from 2 to about 18 carbonatoms, preferably at a ratio of the total number of moles of the atleast one alcohol to the number of moles of the aforesaidmagnesium-containing compound in the range of from about 1.45:1, morepreferably from about 1.6:1, to about 2.3:1, more preferably to about2.1:1. Alcohols that are suitable for use in the present inventioninclude those having the structure HOR wherein R is an alkyl radical of1 to about 18 carbon atoms, an aryl radical of 6 to about 12 carbonatoms or an alkaryl or aralkyl radical of 7 to about 12 carbon atoms.Typically, one or more alcohols containing from 1 to 12 carbon atoms canbe used, such as ethanol, 1- or 2-propanol, t-butyl alcohol,cyclohexanol, 2-ethylhexanol, amyl alcohols including isoamyl alcohol,and branched alcohols having 9 to 12 carbon atoms. Preferably,2-ethylhexanol or ethanol is employed.

In somewhat greater detail, the magnesium-containing species is preparedby dissolving or suspending the magnesium-containing compound in aliquid. Approximately 10 to 80 parts by weight of themagnesium-containing compound is employed per 100 parts by weightliquid. A sufficient amount of carbon dioxide is bubbled into the liquidsuspension to provide from about 0.1 to 4 moles of carbon dioxide permole of the magnesium compound with mild stirring. Typically,approximately 0.3 to 4 moles of CO₂ are added to the solution orsuspension of the magnesium-containing compound with stirring at atemperature of about 0 to 100° C. over a period of approximately 10minutes to 24 hours.

Irrespective of which of the aforesaid magnesium-containing compounds isused to form the magnesium-containing species, solid particles areprecipitated from the aforesaid solution of the magnesium-containingspecies by treatment with a transition metal or Group IV halide andpreferably additionally with a morphology controlling agent. Thetransition metal or Group IV halide preferably is a titanium (IV) orsilicon halide and more preferably is titanium tetrachloride. While anyconvenient conventional morphology controlling agent can be employed,organosilanes are particularly suitable for use as the morphologycontrolling agent. Suitable organosilanes for this purpose include thosehaving a formula: R_(n)SiR′_(4-n), wherein n=0 to 4 and wherein R ishydrogen or an alkyl, alkoxy, haloalkyl or aryl radical containing oneto about ten carbon atoms, or a halosilyl radical or haloalkylsilylradical containing one to about eight carbon atoms, and R′ is OR or ahalogen. Typically, R is an alkyl or chloroalkyl radical containing oneto about eight carbon atoms and one to about four chlorine atoms, and R′is chlorine or an —OR radical containing one to four carbon atoms. Asuitable organosilane may contain different R′ groups. Mixtures oforganosilanes may be used. Preferable organosilanes includetri-methyichlorosilane, trimethylethoxysilane, dimethyldichiorosilane,tetraethoxy-silane, and hexamethyldisiloxane.

Broadly, in accordance with this invention, the precipitated particlesare treated with a transition metal compound and an electron donor.Suitable transition metal compounds which can be used for this purposeinclude compounds represented by the formula T_(a)Y_(b)X_(c-b) whereinT_(a) is a transition metal selected from Groups IV-B, V-B and VI-B ofthe Periodic Table of Elements, Y is oxygen, OR′ or NR′₂; wherein eachR′ is independently hydrogen or hydrocarbyl group of 1 to 20 carbonatoms; X is halogen, preferably chlorine or bromine; c has a valuecorresponding to the valence of the transition metal, T_(a); b has avalue of from 0 to 5 with a value of c-b being from at least 1 up to thevalue of the valence state of the transition metal T_(a). Suitabletransition metal compounds include halide compounds of titanium,zirconium, vanadium and chromium, such as chromyl chloride, vanadiumoxytrichloride, zirconium tetrachloride, vanadium tetrachloride, and thelike.

In addition to supported catalyst components formed from magnesiumalcoholates or magnesium hydrocarbyl carbonates as described above,other magnesium-containing supported components may be produced byreacting titanium halide-containing compounds with magnesium halides,such as magnesium chloride, magnesium oxyhalides, magnesium alkoxides,and the like. In preparation of suitable supported catalysts useful forolefin polymerization, an electron donor material is added duringformation of such component in which a magnesium compound is reactedwith a titanium halide-containing compound as described in the art.Irrespective of the method of formation, the supported catalystcomponents of this invention include the internal electron donormaterial described in this invention.

Titanium (IV) compounds useful in preparation of the catalyst orcatalyst component of this invention are titanium halides andhaloalcoholates having 1 to about 20 carbon atoms per alcoholate groupsuch as methoxy, ethoxy, butoxy, hexoxy, phenoxy, decoxy, naphthoxy,dodecoxy and eicosoxy. Mixtures of titanium compounds can be employed ifdesired. Preferred titanium compounds are the halides andhaloalcoholates having 1 to 8 carbon atoms per alcoholate group.Examples of such compounds include TiCl₄, TiBr₄, Ti(OCH₃)Cl₃,Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)Cl₃, Ti(OC₆H₅)Cl₃, Ti(OC₆H₁₃)Br₃, Ti(OC₈H₁₇)Cl₃,Ti(OCH₃)₂Br₂, Ti(OC₂H₅)₂Cl₂, Ti(OC₆H₁₃)₂Cl₂, Ti(OC₈H₁₇)₂Br₂,Ti(OCH₃)₃Br, Ti(OC₂H₅)₃Cl, Ti(OC₄H₉)₃Cl, Ti(OC₆H₁₃)₃Br, andTi(OC₈H₁₇)₃Cl. Titanium tetrahalides and particularly TiCl₄ are mostpreferred from the standpoint of attaining maximum activity andstereospecificity.

The particles formed as described above, the titanium halide component,and the electron donor components described in this invention arereacted at temperatures ranging from about −10° C. to about 170° C.,generally over a period of several minutes to several hours, and arecontacted in amounts such that the atomic ratio of titanium to magnesiumcomponents in the reaction mixture (calculated as magnesium in magnesiumcompound from which the magnesium-containing species is formed) is atleast about 0.5:1. Preferably, this ratio ranges from about 0.5:1 toabout 20:1. Greater amounts of titanium may be employed withoutadversely affecting catalyst component performance, but typically thereis no need to exceed a titanium to magnesium ratio of about 20:1. Morepreferably, the titanium to magnesium ratio ranges from about 2:1 toabout 15:1 to ensure that the catalyst components contain sufficienttitanium to exhibit good activities without being wasteful of thetitanium compound employed in preparation. The internal electron donorcomponents are employed in a total amount ranging up to about 1.0 moleper gram atom of titanium in the titanium compound, and preferably fromabout 0.001 to about 0.6 mole per gram atom of titanium in the titaniumcompound. Best results are achieved when this ratio ranges from about0.01 to about 0.3 mole per gram atom of titanium.

Preferably, the aforesaid electron donor compounds and titanium compoundis contacted with the precipitated solid particles in the presence of aninert hydrocarbon or halogenated diluent, although other suitabletechniques can be employed. Suitable diluents are substantially inert tothe components employed and are liquid at the temperature and pressureemployed.

Preferably, although optional, the precipitated particles arereprecipitated from a solution containing, typically, a cyclic ether,and then the reprecipitated particles are treated with a transitionmetal compound and an electron donor as described above

In a typical reprecipitation procedure, the precipitated particles areentirely solubilized in a cyclic ether solvent and then particles areallowed to reprecipitate to form particles of uniform size. Thepreferable ether is tetrahydrofuran, although other suitable cyclicethers, such as tetrahydropyran and 2-methyltetrahydrofuran, may beused, which can solubilize the particles. Also, thioethers such astetrahydrothiophene can be used. In some instances, such as the use of2,2,5,5-tetrahydrofuran and tetrahydropyran-2-methanol, reprecipitationoccurs upon heating to about 55°-85° C. Other compounds may be usedwhich act in an equivalent manner, i.e., materials which can solubilizethe particles formed in Step B and from which solid uniform particlescan be reprecipitated, such as cyclohexene oxide, cyclohexanone, ethylacetate and phenyl acetate. Mixtures of such suitable materials may alsobe used.

A suitable diluent that can be used in any of the aforesaid steps shouldbe substantially inert to the reactants employed and preferably isliquid at the temperatures and pressures used. A particular step may beconducted at an elevated pressure so that lower boiling diluents can beused at higher temperatures. Typical suitable diluents are aromatic orsubstituted aromatic liquids, although other hydrocarbon-based liquidsmay be used. Aromatic hydrocarbons, such as toluene, and substitutedaromatics are useful. An especially suitable diluent is a halogenatedaromatic such as chlorobenzene or a mixture of a halogenated aromaticsuch as chlorobenzene and a halogenated aliphatic such asdichloroethane. Also useful are higher boiling aliphatic liquids such askerosene. Mixtures of diluents may be used. One useful diluent componentis Isopar G® which is a C₁₀-average isoparaffinic hydrocarbon boiling at156-176° C. Other examples of useful diluents include alkanes such ashexane, cyclohexane, methylcyclohexane, heptane, octane, nonane, decane,undecane, and the like; haloalkanes such as 1,2-dichloroethane,1,1,2-trichloroethane, carbon tetrachloride and the like; aromatics suchas benzene, toluene, xylenes and ethylbenzene; and halogenated andhydrogenated aromatics such as chlorobenzene and o-di-chlorobenzene.

Each of the aforesaid preparative steps is conducted in the substantialabsence of water, oxygen, carbon monoxide, and other extraneousmaterials capable of adversely affecting the performance of the catalystor catalyst component of this invention. Such materials are convenientlyexcluded by carrying out the procedures in the presence of an inert gassuch as nitrogen or argon, or by other suitable means. Optionally, allor part of the process can be conducted in the presence of one or morealpha-olefins which, when introduced into the preparative system ingaseous form, can serve to exclude catalyst poisons. The presence of oneor more alpha-olefins also can result in improved stereospecificity.Useful alpha-olefins include ethylene, propylene, butene-1, pentene-1,4-methylpentene-1, hexene-1, and mixtures thereof. Of course, anyalpha-olefin employed should be of relatively high purity, for example,polymerization grade or higher. Other precautions which aid in excludingextraneous poisons include purification of any diluent to be employed,such as by percolation through molecular sieves and/or silica gel priorto use, and drying and/or purifying other reagents.

As a result of the above-described preparation steps, there is obtaineda solid reaction product suitable for use as a catalyst or catalystcomponent. Prior to such use, it is desirable to removeincompletely-reacted starting materials from the solid reaction product.This is conveniently accomplished by washing the solid, after separationfrom any preparative diluent, with a suitable solvent, such as a liquidhydrocarbon or chlorocarbon, preferably within a short time aftercompletion of the preparative reaction because prolonged contact betweenthe catalyst component and unreacted starting materials may adverselyaffect catalyst component performance.

Although not required, the final solid reaction product prepared may becontacted with at least one Lewis acid prior to polymerization. SuchLewis acids useful according to this invention are materials which areliquid or soluble in a liquid diluent at treatment temperatures and havea Lewis acidity high enough to remove impurities such as unreactedstarting materials and poorly affixed compounds from the surface of thesolid reaction product. Preferred Lewis acids include halides of GroupIII-V metals which are in the liquid state at temperatures up to about170° C. Specific examples of such materials include BCl₃, AlBr₃, TiCl₄,TiBr₄, SiCl₄, GeCl₄, SnCl₄, PCl₃ and SbCl₅. Preferable Lewis acids areTiCl₄ and SiCl₄. Mixtures of Lewis acids can be employed if desired.Such Lewis acid may be used in a compatible diluent.

Although not required, the final solid reaction product may be washedwith an inert liquid hydrocarbon or halogenated hydrocarbon beforecontact with a Lewis acid. If such a wash is conducted, it is preferredto substantially remove the inert liquid prior to contacting the washedsolid with Lewis acid.

In an advantageous procedure, the precipitated particles are treatedwith titanium tetrachloride and then with titanium tetrachloride in thepresence of the mixture of electron donors. More preferably, the productis treated one or more times with a liquid aromatic hydrocarbon such astoluene and finally with titanium tetrachloride again.

In an embodiment of this invention, a mixture of electron donors isincorporated into the supported catalyst component comprising a firstelectron donor and an additional electron donor. The first electrondonor is selected from the group of electron donors described above asrepresenting the class of electron donors of this invention. The secondelectron donor is a dialkylphthalate wherein each alkyl group may be thesame or different and contains from 3 to 5 carbon atoms. The additionalelectron donor is preferably a dibutylphthalate and more preferably isdi-n-butylphthalate or di-i-butylphthalate. The mole ratio of theadditional electron donor to the first electron donor may range fromabout 0.1:1 to about 20:1, preferably from about 0.3:1 to about 1:1.

Also, the internal electron donor material useful in this invention maybe combined with additional electron donors such as a polyhydrocarbylphosphonate, phosphinate, phosphate or phosphine oxide or an alkylaralkylphthalate, wherein the alkyl moiety contains from 2 to 10,preferably 3 to 6, carbon atoms and the aralkyl moiety contains from 7to 10, preferably to 8, carbon atoms, or an alkyl ester of an aromaticmonocarboxylic acid wherein the monocarboxylic acid moiety contains from6 to 8 carbon atoms and the alkyl moiety contains from 1 to 3 carbonatoms.

Useful polyhydrocarbyl phosphonates, phosphinates, phosphates, orphosphine oxides include:

wherein each hydrocarbyl group (R₁, R₂, and R₃) may be the same ordifferent and may be alkyl or aryl, and each contains from 1 to 12carbon atoms

Preferably each hydrocarbyl group (R₁, R₂ and R₃) is an alkyl group.Preferably a phosphonate is employed. Particular phosphonates that aresuitable for use as an aforesaid preferable component include dimethylmethylphosphonate, diethyl ethylphosphonate, diisopropylmethylphosphonate, dibutylbutylphosphonate, and di(2-ethylhexyl)2-ethylhexyl phosphonate.

The additional component also may be a dialkylphthalate wherein eachalkyl moiety may be the same or different and each contains at least 6carbon atoms, preferably up to 10 atoms. Particular dialkylphthalateswhich are suitable for use as an additional electron donor includedihexylphthalate and dioctylphthalate.

Also, the additional component may be an alkyl ester of an aliphaticmonocarboxylic acid wherein carboxylic acid moiety contains 2 to 20,preferably 3 to 6, carbon atoms and the alkyl moiety contains from 1 to3 carbon atoms. Particular alkyl esters that are suitable for use as theaforesaid first electron donor include methyl valerate, ethyl pivalate,methyl pivalate, methyl butyrate, and ethyl propionate.

In another alternative, the additional component may be adicycloaliphatic ester of an aromatic dicarboxylic acid wherein eachcycloaliphatic moiety may be the same or different and each containsfrom 5 to 7 carbon atoms, and preferably contains 6 carbon atoms.Preferably the ester is a dicycloaliphatic diester of an ortho aromaticdicarboxylic acid. Particular dicycloaliphatic esters that are suitablefor use as the aforesaid first electron donor includedicyclopentylphthalate, dicyclohexylphthalate, anddi-(methylcyclopentyl)-phthalate.

The additional component may be an alkyl aralkyl phthalate wherein thealkyl moiety contains 2 to 10, preferably 3 to 6, carbon atoms, and thearalkyl moiety contains from 7 carbon atoms up to 10, preferably up to8, carbon atoms. Particularly, alkyl aralkyl phthalates suitable for useas an additional component include benzyl n-butyl phthalate and benzyli-butyl phthalate. In another alternative, such additional componentalso may be an alkyl ester of an aromatic monocarboxylic acid whereinthe monocarboxylic acid moiety contains from 6 to 8 carbon atoms and thealkyl moiety contains from 1 to 3 carbon atoms. Particular alkyl estersthat are suitable for use as an additional component include methyltoluate, ethyl toluate, methyl benzoate, ethyl benzoate and propylbenzoate.

The mole ratio of first electron donor component described in thisinvention to the additional component is in the range of from about0.5:1, preferably from about 1:1, to about 3:1, preferably to about2.5:1. The mole ratio of the aforesaid second electron donor to thecombination of the first electron donor and the additional electrondonor ranges from about 4:1, preferably from about 7:1, to about 15:1,preferably to about 9:1.

Although the chemical structure of the catalyst or catalyst componentsof this invention is not known precisely, the components generallycomprise from about 1 to about 6 weight percent titanium, from about 10to about 25 weight percent magnesium, and from about 45 to about 65weight percent halogen. Preferably, the catalyst component of thisinvention comprise from about 2.0 to about 4 weight percent titanium,from about 15 to about 21 weight percent magnesium and from about 55 toabout 65 weight percent chlorine.

In the solid catalyst component of this invention produced by the methodof this invention, the atomic ratio of magnesium to titanium is at leastabout 0.3:1 and preferably, is from about 0.4:1 to about 20:1 and morepreferably, from about 3:1 to about 9:1.

Prepolymerization or encapsulation of the catalyst or catalyst componentof this invention also may be carried out prior to being used in thepolymerization or copolymerization of alpha olefins. A particularlyuseful prepolymerization procedure is described in U.S. Pat. No.4,579,836, which is incorporated herein by reference.

Typically, the catalyst or catalyst component of this invention is usedin conjunction with a cocatalyst component including a Group II or IIImetal alkyl and, typically, one or more modifier compounds. Useful GroupII and IIIA metal alkyls are compounds of the formula MR_(m) wherein Mis a Group II or IIIA metal, each R is independently an alkyl radical of1 to about 20 carbon atoms, and m corresponds to the valence of M.Examples of useful metals, M, include magnesium, calcium, zinc, cadmium,aluminum, and gallium. Examples of suitable alkyl radicals, R, includemethyl, ethyl, butyl, hexyl, decyl, tetradecyl, and eicosyl. From thestandpoint of catalyst component performance, preferred Group II andIIIA metal alkyls are those of magnesium, zinc, and aluminum wherein thealkyl radicals contain 1 to about 12 carbon atoms. Specific examples ofsuch compounds include Mg(CH₃)₂, Mg(C₂H₅)₂, Mg(C₂H₅)(C₄H₉), Mg(C₄H₉)₂,Mg(C₆H₁₃)₂, Mg(C₁₂H₂₅)₂, Zn(CH₃)₂, Zn(C₂H₅)₂, Zn(C₄H₉)₂, Zn(C₄H₉)(C₈H₁₇), Zn(C₆H₁₃)₂, Zn(C₆H₁₃)₃, and Al(C₁₂H₂₅)₃. A magnesium, zinc, oraluminum alkyl containing 1 to about 6 carbon atoms per alkyl radicalmay be used. Aluminum alkyls are preferred and most preferablytrialkylaluminums containing 1 to about 6 carbon atoms per alkylradical, and particularly triethylaluminum and triisobutylaluminum or acombination thereof are used.

If desired, metal alkyls having one or more halogen or hydride groupscan be employed, such as ethylaluminum dichloride, diethylaluminumchloride, diethylaluminum hydride, diisobutylaluminum hydride, and thelike.

A typical catalyst system for the polymerization or copolymerization ofalpha olefins is formed by combining the supported titanium-containingcatalyst or catalyst component of this invention and an alkyl aluminumcompound as a co-catalyst, together with at least one external modifierwhich typically is an electron donor and, preferably, is a silane.Typically, useful aluminum-to-titanium atomic ratios in such catalystsystems are about 10 to about 500 and preferably about 30 to about 300.Typical aluminum-to-electron donor molar ratios in such catalyst systemsare about 2 to about 60. Typical aluminum-to-silane compound molarratios in such catalyst systems are about 3 to about 50.

To optimize the activity and stereospecificity of this cocatalystsystem, it is preferred to employ one or more external modifiers,typically electron donors, and including compounds such as silanes,mineral acids, organometallic chalcogenide derivatives of hydrogensulfide, organic acids, organic acid esters and mixtures thereof.

Organic electron donors useful as external modifiers for the aforesaidcocatalyst system are organic compounds containing oxygen, silicon,nitrogen, sulfur, and/or phosphorus. Such compounds include organicacids, organic acid anhydrides, organic acid esters, alcohols, ethers,aldehydes, ketones, silanes, amines, amine oxides, amides, thiols,various phosphorus acid esters and amides, and the like. Mixtures oforganic electron donors also may be used.

Particular organic acids and esters are benzoic acid, halobenzoic acids,phthalic acid, isophthalic acid, terephthalic acid, and the alkyl estersthereof wherein the alkyl group contains 1 to 6 carbon atoms such asmethyl chlorobenzoates, butyl benzoate, isobutyl benzoate, methylanisate, ethyl anisate, methyl p-toluate, hexylbenzoate, and cyclohexylbenzoate, and diisobutyl phthalate as these give good results in termsof activity and stereospecificity and are convenient to use.

The aforesaid cocatalyst system advantageously and preferably containsan aliphatic or aromatic silane external modifier. Preferable silanesuseful in the aforesaid cocatalyst system include alkyl-, aryl-, and/oralkoxy-substituted silanes containing hydrocarbon moieties with 1 toabout 20 carbon atoms. Especially preferred are silanes having aformula: SiY₄, wherein each Y group is the same or different and is analkyl or alkoxy group containing 1 to about 20 carbon atoms. Preferredsilanes include isobutyltrimethoxysilane, diisobutyldimethoxysilane,diisopropyldimethoxysilane, n-propyltriethoxysilane,isobutylmethyldimethoxysilane, isobutylisopropyledimethoxysilane,dicyclopentyldimethoxysilane, tetraethylorthosilicate,dicyclohexyldimethoxysilane, diphenyldimethoxysilane,di-t-butyldimethoxysilane, and t-butyltrimethoxysilane.

In one aspect of this invention the substituted cycloalkanedicarboxylates identified above as catalyst component internal donorsmay be used as external donors alone or in combination with othersuitable external donors including the above-identified silanecompounds.

The catalyst or catalyst component of this invention is useful in thestereospecific polymerization or copolymerization of alpha-olefinscontaining 3 or more carbon atoms such as propylene, butene-1,pentene-1, 4-methylpentene-1, and hexene-1, as well as mixtures thereofand mixtures thereof with ethylene. The catalyst or catalyst componentof this invention is particularly effective in the stereospecificpolymerization or copolymerization of propylene or mixtures thereof withup to about 30 mole percent ethylene or a higher alpha-olefin. Accordingto the invention, highly crystalline polyalpha-olefin homopolymers orcopolymers are prepared by contacting at least one alpha-olefin with theabove-described catalyst or catalyst component of this invention underpolymerization or copolymerization conditions. Such conditions includepolymerization or copolymerization temperature and time, pressure(s) ofthe monomer(s), avoidance of contamination of catalyst, choice ofpolymerization or copolymerization medium in slurry processes, the useof additives to control homopolymer or copolymer molecular weights, andother conditions well known to persons skilled in the art. Slurry-,bulk-, and vapor-phase polymerization or copolymerization processes arecontemplated herein.

The amount of the catalyst or catalyst component of this invention to beused varies depending on choice of polymerization or copolymerizationtechnique, reactor size, monomer to be polymerized or copolymerized, andother factors known to persons of skill in the art, and can bedetermined on the basis of the examples appearing hereinafter.Typically, a catalyst or catalyst component of this invention is used inamounts ranging from about 0.2 to 0.02 milligrams of catalyst to gram ofpolymer or copolymer produced.

Irrespective of the polymerization or copolymerization process employed,polymerization or copolymerization should be carried out at temperaturessufficiently high to ensure reasonable polymerization orcopolymerization rates and avoid unduly long reactor residence times,but not so high as to result in the production of unreasonably highlevels of stereorandom products due to excessively rapid polymerizationor copolymerization rates. Generally, temperatures range from about 0°to about 120° C. with a range of from about 20° C. to about 95° C. beingpreferred from the standpoint of attaining good catalyst performance andhigh production rates. More preferably, polymerization according to thisinvention is carried out at temperatures ranging from about 50° C. toabout 80° C.

Olefin polymerization or copolymerization according to this invention iscarried out at monomer pressures of about atmospheric or above.Generally, monomer pressures range from about 20 to about 600 psi (140to 4100 kPa), although in vapor phase polymerizations orcopolymerizations, monomer pressures should not be below the vaporpressure at the polymerization or copolymerization temperature of thealpha-olefin to be polymerized or copolymerized.

The polymerization or copolymerization time will generally range fromabout ½ to several hours in batch processes with corresponding averageresidence times in continuous processes. Polymerization orcopolymerization times ranging from about 1 to about 4 hours are typicalin autoclave-type reactions. In slurry processes, the polymerization orcopolymerization time can be regulated as desired. Polymerization orcopolymerization times ranging from about ½ to several hours aregenerally sufficient in continuous slurry processes.

Diluents suitable for use in slurry polymerization or copolymerizationprocesses include alkanes and cycloalkanes such as pentane, hexane,heptane, n-octane, isooctane, cyclohexane, and methylcyclohexane;alkylaromatics such as toluene, xylene, ethylbenzene, isopropylbenzene,ethyl toluene, n-propyl-benzene, diethylbenzenes, and mono- anddialkylnaphthalenes; halogenated and hydrogenated aromatics such aschlorobenzene. Chloronaphthalene, ortho-dichlorobenzene,tetrahydro-naphthalene, decahydronaphthalene; high molecular weightliquid paraffins or mixtures thereof, and other well-known diluents. Itoften is desirable to purify the polymerization or copolymerizationmedium prior to use, such as by distillation, percolation throughmolecular sieves, contacting with a compound such as an alkylaluminumcompound capable of removing trace impurities, or by other suitablemeans.

Examples of gas-phase polymerization or copolymerization processes inwhich the catalyst or catalyst component of this invention is usefulinclude both stirred bed reactors and fluidized bed reactor systems andare described in U.S. Pat. Nos. 3,957,448; 3,965,083; 3,971,786;3,970,611; 4,129,701; 4,101,289; 3,652,527; and 4,003,712, allincorporated by reference herein. Typical gas phase olefinpolymerization or copolymerization reactor systems comprise at least onereactor vessel to which olefin monomer and catalyst components can beadded and which contain an agitated bed of forming polymer particles.Typically, catalyst components are added together or separately throughone or more valve-controlled ports in the single or first reactorvessel. Olefin monomer, typically, is provided to the reactor through arecycle gas system in which unreacted monomer removed as off-gas andfresh feed monomer are mixed and injected into the reactor vessel. Forproduction of impact copolymers, homopolymer formed from the firstmonomer in the first reactor is reacted with the second monomer in thesecond reactor. A quench liquid, which can be liquid monomer, can beadded to polymerizing or copolymerizing olefin through the recycle gassystem in order to control temperature.

Irrespective of polymerization or copolymerization technique,polymerization or copolymerization is carried out under conditions thatexclude oxygen, water, and other materials that act as catalyst poisons.Also, according to this invention, polymerization or copolymerizationcan be carried out in the presence of additives to control polymer orcopolymer molecular weights. Hydrogen is typically employed for thispurpose in a manner well known to persons of skill in the art. Althoughnot usually required, upon completion of polymerization orcopolymerization, or when it is desired to terminate polymerization orcopolymerization or at least temporarily deactivate the catalyst orcatalyst component of this invention, the catalyst can be contacted withwater, alcohols, acetone, or other suitable catalyst deactivators in amanner known to persons of skill in the art.

The products produced in accordance with the process of this inventionare normally solid, predominantly isotactic polyalpha-olefins.Homopolymer or copolymer yields are sufficiently high relative to theamount of catalyst employed so that useful products can be obtainedwithout separation of catalyst residues. Further, levels of stereorandomby-products are sufficiently low so that useful products can be obtainedwithout separation thereof. The polymeric or copolymeric productsproduced in the presence of the invented catalyst can be fabricated intouseful articles by extrusion, injection molding, and other commontechniques.

The polymer component of the composition of this invention primarilycontains a high crystalline polymer of propylene. Polymers of propylenehaving substantial polypropylene crystallinity content now arewell-known in the art. It has long been recognized that crystallinepropylene polymers, described as “isotactic” polypropylene, containcrystalline domains interspersed with some non-crystalline domains.Noncrystallinity can be due to defects in the regular isotactic polymerchain which prevent perfect polymer crystal formation. The extent ofpolypropylene stereoregularity in a polymer can be measured bywell-known techniques such as isotactic index, crystalline meltingtemperature, flexural modulus, and, recently by determining the relativepercent of meso pentads (% m4) by carbon-13 nuclear magnetic resonance(¹³C NMR).

The propylene polymer especially useful in this invention has both ahigh nmr tacticity and a broadened molecular weight distribution (“MWD”)as measured by the ration of the weight average to number averagemolecular weights (M_(w)/M_(n)). Such molecular weights typically aremeasured by gel permeation chromatography (GPC) techniques known in theart. In addition, preferable polymers of this invention have flexuralmoduli above about 1800 MPa and typically above about 2100 MPa. Inaddition the nmr pentad tacticity typically is above 90% and preferablyis above about 95% and may be above about 97%. Typical polymer melt flowrates are 1 to 20 g/10 min.

A method to determine stereoregularity of a propylene polymer uses ¹³CNMR and is based on the ability to identify relative positions ofadjacent methyl groups on a polypropylene polymer backbone. If themethyl groups of two adjacent propylene monomer units (—CH(CH₃)—CH₂—)are on the same side of the polymer chain, such two methyl groups form ameso (“m”) dyad. The relative percentage of these meso dyads isexpressed as %m. If the two methyl groups of adjacent monomer units areon opposite sides of the polymer chain, such two methyl groups form aracemic (“r”) dyad, and the relative percentage of these racemic dyadsis expressed as % r. Advances in ¹³C NMR techniques permit measurementof the relative positioning of three, four, and five successive methylgroups, which are referred to as triads, tetrads and pentads,respectively.

Current NMR instruments can quantify the specific distribution ofpentads in a polymer sample. There are ten unique pentads which arepossible in a propylene polymer:

m m m m r r r r m m m r m m r m m m r r m r r m r m m r r m r m r m r rm r r r

A ball and stick representation of the mmmm pentad is:

-   -   m m m m    -   -i-i-i-i-i-

Two of the possible pentads cannot be separated by NMR (mmrm and rmmr)and are reported together. Two of the ten pentads (mmrr and mrrm) resultfrom the displacement of a single methyl group on the opposite side ofthe polymer chain in an isotactic sequence. Since the mmmm (m4) pentadrepresents a perfect isotactic stereoregular structure, measurement ofthis pentad (as % m4) reflects isotacticity and potential crystallinity.As used herein, the term NMR tacticity index is the percent of m4 (% m4)pentads as measured by ¹³C NMR. Thus, if 96% of pentads measured by ¹³CNMR in a propylene polymer are m4, the NMR tacticity index is 96.

The invention described herein is illustrated, but not limited, by thefollowing examples.

EXAMPLES

A series of supported catalyst components are prepared using variousmixtures of internal electron donors. Examples using electron donors ofthis invention are described below, together with Comparative Runs notusing such internal electron donors.

Step A—Formation of Magnesium Alkyl Carbonate Solution

Into a two-liter reactor, equipped with a mechanical stirrer and flushedwith dry nitrogen, is transferred a mixture of 153 grams of magnesiumethoxide, 276 milliliters of 2-ethyl-1-hexanol and 1100 milliliters oftoluene. This mixture is agitated at 450 rpm under 30 psig of carbondioxide and heated at 93° C. for three hours. The resulting solution(1530 milliliters) is transferred to a two-liter bottle. The solutioncontains 0.10 gram-equivalents of magnesium ethoxide per milliliter.

Step B—Formation of Solid Particles

Into a 1.0-liter reactor is charged 150 milliliters of toluene, 20.5milliliters of tetraethoxysilane, and 14 milliliters of titaniumtetrachloride under a blanket of dry nitrogen. After the mixture isstirred at 300 rpm at 22-27° C. for 15 minutes, 114 milliliters of theStep A magnesium hydrocarbyl carbonate solution is added to the reactorthrough a bomb and thereafter solid particles precipitate.

Step C—Reprecipitation

After the mixture containing the precipitate is stirred for fiveadditional minutes, 27 milliliters of tetrahydrofuran (THF) were addedrapidly through a syringe. The temperature in the reactor rises from 26°C. to 38° C. Whereupon, the stirring is maintained at 300 rpm and thetemperature is increased to 60° C. within 15 minutes. The first formedsolid dissolves in the THF solution. Within about 5 minutes after theTHF addition, a solid begns to reprecipitate from solution. Stirring iscontinued for 1 hour at 60° C. after which agitation is stopped and theresulting solid is allowed to settle. Supernatant is decanted and thesolid washed two times with 50-milliliter portions of toluene.

Step D—Titanium (IV) Compound Treatment

To the solid from Step C in the one-liter reactor are added 125milliliters of toluene and 50 milliliters of titanium tetrachloride. Theresulting mixture is heated to 116° C. within 30 minutes and stirred at300 rpm for one hour. After stirring is stopped, the resulting solid isallowed to settle and the supernatant is decanted. After 150 millilitersof toluene, 50 milliliters of titanium tetrachloride, the electron donorcompounds of this invention are added to the resulting solid, themixture is stirred at 300 rpm at 117° C. for 90 minutes, the solid isallowed to settle and supernatant liquid is decanted. After 95milliliters of toluene are added, the mixture is heated to 91° C. for 30minutes. After the agitation is stopped, the solid is allowed to settleand the supernatant decanted. An additional 125 milliliters of titaniumtetrachloride are added, the mixture is heated at 91° C. under agitationfor 30 minutes, after which the agitation is stopped, and thesupernatant liquid is decanted. The residue is washed four times with50-milliliter portions of hexane and the solids are recovered. The moleratio of magnesium/titanium/electron donor components in the reactantsfor the examples is 1/5/0.45.

Batch slurry phase propylene polymerization evaluation is performed in atwo liter reactor at 71° C. at a total reactor pressure of 150 poundsper square inch gauge with 7 millimoles of hydrogen, while stirring at500 revolutions per minute with a reaction time of 2 hours.Triethylaluminum (TEA) is used as a co-catalyst together withdiisobutyldimethoxysilane as an external modifier. The reactor ischarged with TEA/modifier, titanium component, hydrogen, and propylenein that order.

In a typical procedure, a dry, nitrogen-purged, two-liter stainlesssteel autoclave reactor was charged with catalyst (˜20 mg),triethylaluminum (3.6 mL of a 0.75 M solution in heptane), anddiisobutyldimethoxysilane (1.0 mL of a 0.15 M solution in heptane), and850 mL of heptane at 40 C. Hydrogen was introduced at 12.5 psig.Agitation and heating was started and a 15 psig pressure drop from a 75mL vessel containing hydrogen was introduced to the reactor followed byan approximately 30 gram portion of propylene. When the temperaturereaches 70 C, the propylene reservoir to the reactor was opened and aconstant propylene pressure of 150 psig is maintained for one hour. Thereactor was then vented and the resulting polymer slurry dumped from thereactor, filtered and dried. Analysis was performed after oven dryingand weighing of the polymer powder.

Catalyst components were prepared in a manner consistent with theabove-described procedure using various internal donors. Test runs usingvarious internal modifiers are shown in Table 1.

TABLE 1 Yield MFR Bulk (g/g (g/10 Density XS Mn Mw Mz Mz + 1 RunModifier Structure PP) min) (g/cc) (wt. %) (X 10⁻³) (X 10⁻³) (X 10⁻³)(x10⁻³) M_(w)/M_(n) M_(z)/M_(w) 1

8160 8.40 0.425 2.7 50.2 272 894 2053 5.42 3.29 2

6080 11.68 0.397 4.78 44.6 259 917 2128 5.81 3.54  3*

5390 10.60 0.405 5.35 46.2 264 943 2173 5.71 3.57 4

3370 11.76 0.337 5.9 49.6 258 984 2505 5.20 3.81 5

5330 11.55 0.39 6.47 44.4 261 1009 2465 5.88 3.87 6

“Yield” (grams of polymer produced per gram of solid catalyst component)is based on the weight of solid catalyst used to produce polymer.“Solubles” are determined by evaporating the solvent from an aliquot offiltrate to recover the amount of soluble polymer produced and arereported as the weight percent (% Sol.) of such soluble polymer based onthe sum of the weights of the solid polymer isolated by filtration andof the soluble polymer. “Xylene Solubles” (“XS”) are Solubles usingboiling xylenes as the solvent. “Extractables” are determined bymeasuring the loss in weight of a dry sample of ground polymer afterbeing extracted in boiling n-hexane for three to six hours and arereported as the weight percent (% Ext.) of the solid polymer removed bythe extraction. The bulk density (BD) is reported in units of pounds percubic foot (1 lbs/ft³=0.0149 g/ml). The viscosity of the solid polymerwas measured according to ASTM D1238 Condition L (2.16 kg©230° C.) andreported as the melt flow rate (MFR) in grams of polymer per 10 minutes.

Decalin Solubles (“DS”) is a measure of hydrocarbon soluble andextractable materials, such as atactic, non-crystalline, and oligomericcomponents, contained in a propylene polymer and is useful incorrelating a particular resin to desirable resin properties such asprocessing window. DS is determined by completely dissolving a 2.0-gramsample of polymer in 100 milliliters of Irganox 1076-stabilized (0.020grams/liter) decalin (decahydronaphthalene) by warming the slurry to165° C. and stirring the slurry for two hours. Once the polymer isdissolved, the solution is allowed to cool overnight (at least 16hours). After the cooling period, the solution is filtered from theprecipitated polymer. A measured portion of the solution is withdrawnand, after removing the decalin solvent, the resulting samples arecompletely dried in a 120° C. vacuum oven. The final dried samples areweighed to determine the amount of decalin-soluble polymer. Results arereported as a weight percent polymer remaining soluble in decalin.

In order to demonstrate this invention further, propylenepolymerizations are conducted in a laboratory gas-phase reactor using amagnesium halide supported HAC catalyst component produced in accordancewith U.S. Pat. No. 4,886,022. The catalyst component contains 17.32 wt.% magnesium and 2.29 wt % titanium. Triethylaluminum is used as theco-catalyst. The amount of silane modifier is controlled in thepolymerizations such that the Al/Si ratio was in the range 6 to 24 andthe target melt flow rate (MFR) of the polymer is 1 to 50. Thesepropylene polymerizations are performed in a one-gallon (3.8-liter)continuous, horizontal, cylindrical gas-phase reactor measuring 10 cm indiameter and 30 cm in length based on that described in U.S. Pat. No.3,965,083. The reactor is equipped with an off-gas port for recyclingreactor gas through a condenser and back through a recycle line to therecycle nozzles in the reactor. Propylene liquid is used as the quenchliquid to help remove the heat generated in the reactor during thepolymerization. During operation, polypropylene powder produced in thereactor bed, passes over a weir, and was discharged through a powderdischarge system into a secondary closed vessel blanketed with nitrogen.The polymer bed is agitated by paddles attached to a longitudinal shaftwithin the reactor that was rotated at about 75 rpm. The reactorpressure is maintained 300 psig (2100 kPa). Thetitanium/magnesium-containing catalyst was introduced into the reactoras a 1.5 wt % slurry in heptane through a liquid propylene-flushedcatalyst addition nozzle. A mixture of the silane modifier andtriethylaluminum in heptane at Al/Mg and Al/Si molar ratios indicated inTable I are fed separately to the reactor through a liquidpropylene-flushed co-catalyst addition nozzle. Hydrogen was fed to thereactor. Production rate is about 200 g/hr.

1. A solid, hydrocarbon-insoluble, catalyst component containingmagnesium, titanium, and halogen further containing an internal electrondonor comprising a substituted hydrocarbyl 4-8 membered cycloalkanedicarboxylate wherein the substituents are positioned on the cycloalkaneto place the dicarboxylate groups into conformational proximitypositions and wherein the substituents contain 1 to 20 carbon atoms andmay be joined to the cycloalkane structure to form a bicyclo structure.2. The catalyst component of claim 1 wherein the internal electron donoris

in which one X and one Y are carboxylate (CO₂R) groups, wherein R isselected from lower alkyl groups containing 1 to 20 carbon atoms; R1-R8are selected from bulky and non-bulky alkyl or substituted alkyl groupsto produce a ring conformation that places the carboxylate groups intoproximity; and remaining the X and Y groups are selected from hydrogenand methyl, and provided two of the R1-R8 groups may be connected toform a bicyclo structure.
 3. The catalyst component of claim 1 whereinthe internal electron donor is

wherein R is selected from lower alkyl groups containing 1 to 20 carbonatoms, R1 and R4 are selected from bulky groups sufficient to place thecarboxyl groups into conformational proximity positions, and R2 and R4are selected from hydrogen and methyl.
 4. The catalyst component ofclaim 1 wherein the internal electron donor istrans-di-n-butyl-4,5-di-isopropylcyclohexane trans-dicarboxylate ortrans-diisopropyl 4,5-di-t-butylcyclohexane trans-dicarboxylate.
 5. Thecatalyst component of claim 1 wherein the internal electron donor is

wherein R is selected from lower alkyl groups containing 1 to 20 carbonatoms, R1, R3, and R6 are selected from bulky groups sufficient to placethe carboxyl groups into conformational proximity positions, and R2, R4,and R5 are selected from hydrogen and methyl.
 6. The catalyst componentof claim 1 wherein the internal electron donor is

wherein R is selected from lower alkyl groups containing 1 to 20 carbonatoms.
 7. The catalyst component of claim 1 wherein the internalelectron donor is

wherein R is selected from lower alkyl groups containing 1 to 20 carbonatoms.
 8. The catalyst component of claim 1 wherein R is ethyl, propyl,isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl,hexyl, 2-ethylhexyl, or octyl.
 9. The catalyst component of claim 1wherein R contains 3 to 8 carbon atoms.
 10. The catalyst component ofclaim 1 wherein R is ethyl, propyl, isopropyl, n-butyl, isobutyl, ors-butyl.
 11. The catalyst component of claim 1 at least one bulkysubstituent group contains 3 to 20 carbon atoms.
 12. The catalystcomponent of claim 1 at least one of isopropyl, isobutyl, t-butyl,s-butyl, isopentyl, isohexyl, or 2-ethylhexyl.
 13. The catalystcomponent of claim 1 at least one of isopropyl, isobutyl, t-butyl, ors-butyl.
 14. The catalyst component of claim 1 at least one bulkysubstituent group contains a hetero atom.
 15. A olefin polymerizationcatalyst system comprising a solid, hydrocarbon insoluble componentcontaining magnesium, titanium, and halogen and an internal electrondonor compound, an aluminum alkyl compound, and an external electrondonor compound comprising a substituted hydrocarbyl 4-8 memberedcycloalkane dicarboxylate wherein the substituents are positioned on thecycloalkane to place the dicarboxylate groups into conformationalproximity positions and wherein the substitutes contain 1 to 20 carbonatoms and may be joined to the cycloalkane structure to form a bicyclostructure.